EP1695692A2 - Composition containing a fatty alcohol wax and a cellulose polymer for application upon keratin fibres - Google Patents

Abstract

Keratinous fiber coating composition (A), comprises a fatty phase (I) comprising a fatty alcohol wax (Ia) and a cellulose polymer (Ib) in a medium (II).

Description

The present invention relates to a cosmetic composition for coating keratinous fibers comprising a fatty alcohol wax and a cellulosic polymer.

The composition according to the invention may be a make-up composition, also called mascara, a makeup base for keratinous fibers or a base-coat, a composition to be applied to a make-up, also called a top-coat, or even a treatment composition. keratinous fibers.
Preferably, the composition according to the invention is a non-rinsed composition.

More specifically, the composition according to the invention is a mascara.
By mascara is meant a composition intended to be applied to the eyelashes: it may be a makeup composition of the eyelashes, a makeup base of the eyelashes, a composition to be applied to a mascara, also called top coat, or else a composition for cosmetic treatment of the eyelashes. Mascara is especially intended for human eyelashes, but also false eyelashes.

The makeup compositions for the eyelashes generally consist of a wax or mixture of waxes dispersed with at least one surfactant in an aqueous phase containing, moreover, polymers and pigments.
It is generally through the qualitative and quantitative choice of waxes and polymers that the application specificities sought for makeup compositions, such as, for example, their fluidity, their covering power and / or their curling power, are adjusted. Thus, it is possible to produce various compositions which, applied in particular to the eyelashes, induce various effects such as elongation, bending and / or thickening (loading effect).

The present invention aims more particularly to provide a composition useful for making a thick makeup of keratinous fibers and in particular eyelashes, said still makeup charging. For the purpose of the present invention, the term "keratin fibers" covers the hair, eyelashes and eyebrows and also extends to synthetic hairpieces and false eyelashes.

It is known from the prior art that the higher the solids content (provided in part by a fatty phase consisting of, for example, one or more waxes or one or more lipophilic polymers) in a composition will increase, the more the deposit material on the eyelash will be important and therefore the result will be volumizing.

Nevertheless, the increase in the solids content in a composition, such as an emulsion or dispersion results in an increase in the consistency of the product obtained and therefore an application to the eyelashes which is difficult and difficult because the product is thick and viscous. difficult to deposit, heterogeneously and in packets and the makeup thus obtained has a granular appearance, not smooth; the makeup is not homogeneous and has an unsightly appearance.
This is usually the case of so-called volumizing mascaras that are difficult to apply and give a heterogeneous makeup.
It is known from the prior art volumizing mascaras comprising an aqueous phase, a cellulosic polymer and polar waxes such as carnauba wax and / or candellila and having easy application and homogeneous deposition.

The object of the present invention is to propose another formulation pathway for a keratin fiber coating composition that leads to an effect that loads keratinous fibers and that solves all or part of the problems related to conventional formulation routes.
Unexpectedly, it has been found that it was possible to prepare compositions allowing thickening makeup of keratinous fibers and a smooth and homogeneous deposition on said fibers by virtue of the use, in these compositions, of the combination of a fatty alcohol wax and a cellulosic polymer.

The invention thus has, according to one of its aspects, a composition for coating keratinous fibers comprising a cosmetically acceptable aqueous medium characterized in that it comprises at least 3% of at least one fatty alcohol wax and a polymer cellulose.

Another subject of the invention is a composition for coating keratinous fibers comprising a cosmetically acceptable aqueous medium characterized in that it comprises at least one fatty alcohol wax, at least one cellulosic polymer and at least one anionic surfactant.

The present invention also relates to a process for making up keratin fibers, characterized in that a composition according to the invention is applied to said fibers.

It also relates to the use of a composition according to the invention to obtain makeup charging keratinous fibers including eyelashes and eyebrows and / or a smooth and homogeneous deposit on said fibers.

The present invention also relates to the use of the combination of at least one fatty alcohol wax and a cellulosic polymer to obtain makeup charging keratinous fibers including eyelashes and eyebrows and / or a smooth deposit and homogeneous on said fibers.

For the purposes of the present invention, the term "charging" is intended to mean the concept of a thick, volumizing makeup of keratinous fibers, in particular eyelashes.

The compositions according to the invention advantageously have a solids content greater than or equal to 40% by weight, preferably greater than or equal to 42% by weight, better still, greater than or equal to 45% and even better than or equal to 47%. relative to the total weight of the composition, up to 60% by weight.

The dry matter content, that is to say the non-volatile matter content, can be measured in various ways, for example oven drying methods, drying methods by exposure to infrared radiation as well as than the chemical methods by Karl Fischer water titration.
Preferably, the amount of dry matter, commonly called "dry extract" of the compositions according to the invention, is measured by heating the sample with infrared rays of 2 μm to 3.5 μm wavelength. The substances contained in said compositions which have a high vapor pressure, evaporate under the effect of this radiation. The measurement of the loss of weight of the sample makes it possible to determine the "dry extract" of the composition. These measurements are carried out using a Mettler LP16 commercial infrared desiccator. This technique is perfectly described in the documentation of the device supplied by Mettler.
The measurement protocol is as follows:
About 1 g of the composition is spread on a metal cup. This, after introduction into the desiccator, is subjected to a temperature of 120 ° C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance.
The dry matter content is calculated as follows:
Dry extract = 100 x (dry mass / wet mass).

Wax Alcohol aras

For the purposes of the present invention, the term "wax" generally means a lipophilic compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting point of greater than or equal to 30 ° C. up to 120 ° C.
By bringing the wax to the liquid state (fusion), it is possible to render it miscible with oils and to form a microscopically homogeneous mixture, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax is obtained in the oils of the mixture.
In particular, the waxes that are suitable for the invention may have a melting point of greater than about 45 °, more preferably greater than or equal to 50 ° C. and in particular greater than or equal to 55 ° C.
The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2929 by the company TA Instruments.
The measurement protocol is as follows:
A sample of 5 mg of product placed in a crucible is subjected to a first temperature rise from 0 ° C to 120 ° C, at the heating rate of 10 ° C / minute, then is cooled from 120 ° C to 0 ° C. ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise from 0 ° C to 120 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the product sample is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The fatty alcohol waxes may be chosen from saturated or unsaturated, branched or unbranched fatty alcohols containing from 20 to 60 carbon atoms, or mixtures comprising at least 30% of said fatty alcohols, for example with polyethylene.

The fatty alcohols may be linear, they may comprise, for example, from 14 to 60, preferably from 20 to 58 carbon atoms, and preferably correspond to the following chemical formula:

CH3- (CH2) n-CH20H

wherein n is an integer ranging from 16 to 58, preferably from 18 to 56.

Among the branched fatty alcohols, fatty alcohols comprising from 24 to 80 carbon atoms will be preferred.

Such C20-60 fatty alcohols are commercially available, for example, from NEW PHASE TECHNOLOGIES under the names PERFORMACOL® 350, PERFORMACOL® 425, PERFORMACOL® 550 and PERFORMACOL® 700, or from the company PETROLITE under the names UNILIN® 350 Alcohol, UNILIN® 425 Alcohol, UNILIN® 550 Alcohol and UNILIN® 700 Alcohol. They are mixtures of very long chain linear alcohols obtained by a polymerization process making it possible to obtain polymers with a very low polydispersity index (Mw / Mn = 1.1). Their weight average molar mass is between about 350 and 1000.
There may also be mentioned behenyl alcohol, cetyl alcohol, stearyl alcohol and mixtures thereof.

The fatty alcohol may be present in a content ranging from 3 to 50% by weight, preferably from 5 to 40%, better still from 7 to 30% by weight and even more preferably from 10 to 30% relative to the total weight of the composition.

Additional wax

The composition according to the invention may comprise at least one additional wax.

The additional wax may be chosen from waxes which are solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin, and mixtures thereof.

The additional wax may also have a hardness of from 0.05 MPa to 30 MPa. The hardness is determined by measuring the compressive force measured at 20 ° C. using the texturometer sold under the name TA-XT2 by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm. moving at the measuring speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm.
The measurement protocol is as follows:
The wax is melted at a temperature equal to the melting point of the wax + 10 ° C. The melted wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C) for 24 hours so that the surface of the wax is flat and smooth, then the wax is kept for at least 1 hour at 20 ° C before making the measurement. hardness or stickiness.

The mobile of the texturometer is moved at a speed of 0.1 mm / s, then penetrates into the wax to a penetration depth of 0.3 mm. When the mobile penetrated into the wax to the depth of 0.3 mm, the mobile is held stationary for 1 second (corresponding to the relaxation time) and is removed at a speed of 0.5 mm / s.
The hardness value is the maximum measured compressive force divided by the surface of the texturometer cylinder in contact with the wax.

In particular, it is possible to use hydrocarbon-based waxes such as beeswax, lanolin wax, lemon wax, orange wax, and Chinese insect waxes; rice wax, carnauba wax, candelilla wax, ouricurry wax, japanese wax, berry wax, shellac wax and sumac wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, polymethylene waxes, waxes obtained by the Fisher-Tropsch synthesis and waxy copolymers and their esters.
Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains.
Among these, there may be mentioned hydrogenated jojoba oil, isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by Desert Whale under the trade reference ISO-JOJOBA-50 ®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di- (1,1,1-trimethylolpropane) tetrastearate sold under the name " HEST 2T-4S "by the company HETERENE, di- (1,1,1-trimethylolpropane) tetraprenate sold under the name HEST 2T-4B by the company HETERENE.
Mention may also be made of silicone waxes and modified silicone waxes, for example silicone candelilla wax or fluorinated waxes.
It is also possible to use the wax obtained by hydrogenation of esterified olive oil with the stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or even the waxes obtained by hydrogenation of castor oil esterified with alcohol. cetyl sold under the name "PHYTOWAX ricin 16L64 and 22L73" by the company SOPHIM. Such waxes are described in application FR-A-2792190.

According to one embodiment, the wax has a hardness of less than 4 MPa, preferably less than or equal to 3.5 MPa.
Such waxes are, for example, oxypropylenated lanolin wax (50E), orange wax, lemon wax, hydrogenated castor oil wax, the mixture of aliphatic acid esters and primary alcohols marketed under the reference BURCO LB-02, olive wax (unsaponifiables of hydrogenated olive oil) sold under the reference INHOLIVE by the company EXA International, the behenyl methacrylate wax PDMS sold under the reference KP-562 by the company. SHIN ETSU, fluoropolymethyl alkyl dimethylsiloxane wax such as that sold under the reference WAX 23087 by the company Wacker, the C30-C45 alkyl dimethicone wax such as that marketed under the reference SF 1642 by GE Bayer, ditrimethylol propane tetrastearate; ethoxylated (50E) or some paraffin waxes such as the wax marketed under the reference CERAFINE 56/58 by the company BAERLOCHER.

According to a particular embodiment, the additional wax is a so-called sticky wax that is to say having a tack greater than or equal to 0.1 Ns
The tacky wax used may in particular have a tack ranging from 0.1 Ns to 10 Ns, in particular ranging from 0.1 Ns to 5 Ns, preferably ranging from 0.2 to 5 Ns and better still from 0.3 to 2 Ns
The stickiness of the wax is determined by measuring the evolution of the force (compressive force) as a function of time, at 20 ° C. according to the protocol indicated previously for the hardness.
During the relaxation time of 1 s, the force (compressive force) decreases sharply until it becomes zero and then, when the mobile is withdrawn, the force (stretching force) becomes negative and then increases again to the value 0 The tack is the integral of the force vs time curve for the part of the curve corresponding to the negative values of the force. The value of the pantyhose is expressed in Ns

The tacky wax that can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa.
The hardness is measured according to the protocol described above.

As sticky wax, a C ₂₀ -C ₄₀ alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms) can be used, alone or as a mixture
Such a wax is sold, for example, under the names "Kester Wax K 82 P®" and "Kester Wax K 80 P®" by the company Koster Keunen.

The composition according to the invention may comprise a total content of waxes (fatty alcohol wax and additional wax (es)) ranging from 1% to 50% by weight relative to the total weight of the composition, preferably from 5% to 40% by weight. % by weight, in particular it may contain from 10 to 35%, more particularly from 10 to 30%.

The wax (s) (including sticky wax) may be present as an aqueous microdispersion of wax. By aqueous microdispersion of wax is meant an aqueous dispersion of wax particles in which the size of said wax particles is less than or equal to about 1 μm.

Microdispersions of wax are stable dispersions of colloidal wax particles, and are especially described in "Microemulsions Theory and Practice", LM Prince Ed., Academic Press (1977) pages 21-32.
In particular, these microdispersions of wax can be obtained by melting the wax in the presence of a surfactant, and optionally a portion of the water, and then gradually adding hot water with stirring. The intermediate formation of a water-in-oil emulsion is observed, followed by a phase inversion with final obtaining of an oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal particles of wax is obtained.
The microdispersion of wax can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high pressure homogenizer, turbines.

The particles of the microdispersion of wax preferably have average dimensions of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably less than 0.5 μm (in particular ranging from 0.06 μm to 0 μm). , 5 μm).
These particles consist essentially of a wax or a mixture of waxes. However, they may comprise, in a minor proportion, oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active agent.

When the wax or the mixture of waxes is present in the compositions according to the invention, in the form of an aqueous dispersion of particles, the particle size, expressed as the average "effective" diameter by volume D [4.3] as defined below, may advantageously be less than or equal to 1 μm and in particular less than or equal to 0.75 μm.
The wax particles may have various shapes. They can in particular be spherical.

Cellulosic polymer

Preferably, the cellulosic polymer is film-forming. By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials, and preferably a cohesive film and better still, a film whose cohesion and the mechanical properties are such that said film can be isolated from said support.

By cellulosic polymer is meant cellulose or a cellulose derivative.
The cellulosic polymer may be chosen from alkylcelluloses such as methylcellulose, hydroxyalkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose and ethylhydroxyethylcellulose, carboxyalkylcelluloses such as carboxymethylcellulose and mixtures thereof.

The cellulosic polymer may be present in the composition according to the invention in a solids content ranging from 0.1% to 30% by weight relative to the total weight of the composition, preferably from 0.5% to 20% by weight. weight, and better from 1% to 15% by weight.

The composition according to the invention may comprise, in addition to the cellulosic polymer, an additional film-forming polymer.

The additional film-forming polymer may be present in the composition according to the invention in a dry matter content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably from 0.5% to 40%. by weight, and more preferably from 1% to 30% by weight.

Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.

By radical-forming film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates).
The radical-type film-forming polymers may in particular be polymers, or copolymers, vinylic polymers, in particular acrylic polymers.

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers.

As monomer bearing an acid group, it is possible to use α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid.

The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C ₁ -C ₃₀ alkyl (meth) acrylates. , preferably C ₁ -C ₂₀ , aryl (especially) C ₆ -C ₁₀ aryl (meth) acrylates, hydroxyalkyl (meth) acrylates, in particular C ₂ -C hydroxyalkyl (meth) acrylates, ₆ .
Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.
Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.
Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

Amides of the acidic monomers include, for example, (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular C ₂ -C ₁₂ alkyls. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrenic monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.
Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. Styrene monomers include styrene and alpha methyl styrene.

Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

The polyurethanes may be chosen from anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, poly-urethanes-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and their polyurethanes. mixtures.

The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.
The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-acid. dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-acid, cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. A diol chosen from among: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is preferably used. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane.

The polyester amides can be obtained in a similar manner to the polyesters by polycondensation of diacids with diamines or amino alcohols. As the diamine, there can be used ethylenediamine, hexamethylenediamine, meta or para-phenylenediamine. As aminoalcohol, monoethanolamine can be used.

The polyester may further comprise at least one monomer bearing at least one -SO ₃ M group, with M representing a hydrogen atom, an ammonium ion NH ₄ ⁺ or a metal ion, such as for example an ion Na ⁺ , Li ⁺ , K +, Mg ²⁺ , Ca ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ . We may use in particular a bifunctional aromatic monomer comprising such a group -SO ₃ M.

The aromatic nucleus of the bifunctional aromatic monomer additionally bearing a -SO ₃ M group as described above may be chosen for example from benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl and methylenediphenyl nuclei. An example of a bifunctional aromatic monomer also bearing an -SO ₃ M group is sulfoisophthalic acid, sulfoterephthalic acid, sulphophthalic acid and 4-sulphonaphthalene-2,7-dicarboxylic acid.
It is preferred to use copolymers based on isophthalate / sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid.

• les protéines comme les protéines d'origine végétale telles que les protéines de blé, de soja ; les protéines d'origine animale tels que les kératines, par exemples les hydrolysats de kératine et les kératines sulfoniques ;
• les polymères de chitine ou de chitosane anioniques, cationiques, amphotères ou non-ioniques ;
• les polymères vinyliques, comme les polyvinylpyrrolidones, les copolymères de l'éther méthylvinylique et de l'anhydride malique, le copolymère de l'acétate de vinyle et de l'acide crotonique, les copolymères de vinylpyrrolidone et d'acétate de vinyle ; les copolymères de vinylpyrrolidone et de caprolactame ; l'alcool polyvinylique;
• les polymères d'origine naturelle, éventuellement modifiés, tels que:
  • les gommes arabiques, la gomme de guar, les dérivés du xanthane, la gomme de karaya ;
  • les alginates et les carraghénanes ;
  • les glycoaminoglycanes, l'acide hyaluronique et ses dérivés;
  • la résine shellac, la gomme de sandaraque, les dammars, les élémis, les copals ;
  • l'acide désoxyribonuciéïque ;
  • les muccopolysaccharides tels que l'acide hyaluronique, les chondroïtines sulfate, et leurs mélanges.

The composition may comprise a water-soluble film-forming polymer chosen from:

• proteins such as proteins of plant origin such as wheat proteins, soya; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates;
• anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
• vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;
• polymers of natural origin, possibly modified, such as:
  • gum arabic, guar gum, xanthan derivatives, karaya gum;
  • alginates and carrageenans;
  • glycosaminoglycans, hyaluronic acid and its derivatives;
  • shellac resin, sandaraque gum, dammars, elemis, copals;
  • deoxyribonucleic acid;
  • mucopolysaccharides such as hyaluronic acid, chondroitin sulphates, and mixtures thereof.

According to one embodiment of the composition according to the invention, the film-forming polymer may be a polymer solubilized in a liquid organic medium of the composition comprising organic oils or solvents such as those described below (it is said that the film-forming polymer is a fat-soluble polymer).

As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group).

These copolymers may be crosslinked using crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. divinyl.

Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinylether , vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate of vinyl vinyl / allyl acetate, 2,2-dimethyl-2 vinyl octanoate / vinyl laurate, 2,2-dimethyl-2-allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, dimethyl allyl propionate / stearate vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% of tetraally loxyethane, vinyl acetate / allyl stearate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 cross-linked with 0.2% divinyl benzene and allyl propionate / allyl stearate crosslinked with 0 2% divinyl benzene.

Liposoluble film-forming polymers that may also be mentioned include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of vinyl polycrystearate, vinyl polystearate crosslinked with divinylbenzene, diallyl ether or diallyl phthalate, copolymers of stearyl poly (meth) acrylate, polyvinylpolate , poly (meth) acrylate lauryl, these poly (meth) acrylates can be crosslinked using dimethacrylate ethylene glycol or tetraethylene glycol.

The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

As fat-soluble film-forming polymers that can be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C ₂ -C ₂₀ alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated with C ₁ at C _8, such as ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C ₂ to C ₄₀ and better still C ₃ to C ₂₀ alkene. By way of example of a copolymer of VP which may be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, polyvinylpyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid, VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

The film-forming polymer may also be present in the composition in the form of particles dispersed in an aqueous phase or in a non-aqueous solvent phase (liquid organic medium of the composition), generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.
As the aqueous dispersion of film-forming polymer, it is possible to use the acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl® BT-62®, Neocryl A-1079® and Neocryl A- 523® by the company AVECIA-NEORESINS, Dow Latex 432® by the company DOW CHEMICAL, Daitosol 5000 AD® or Daitosol 5000 SJ® by the company DAITO KASEY KOGYO; Syntran 5760® by the company Interpolymer or the aqueous polyurethane dispersions sold under the names Neorez R-981® and Neorez R-974® by the company Avecia-Neoresins, the Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure 2060® by the company GOODRICH, Impranil 85® by the company BAYER, Aquamere H-1511® by the company HYDROMER; sulfopolyesters sold under the trade name Eastman AQ® by Eastman Chemical Products, vinyl dispersions such as Mexomère PAM® from Chimex and mixtures thereof.

The composition according to the invention may comprise a plasticizer promoting the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from all compounds known to those skilled in the art as being capable of performing the desired function.

A cosmetically acceptable aqueous medium

The cosmetically acceptable aqueous medium of the composition according to the invention may consist essentially of water; it may also comprise a mixture of water and of a water-miscible solvent (miscibility in water greater than 50% by weight at 25 ° C.), such as lower monoalcohols having from 1 to 5 carbon atoms, such as ethanol, isopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C ₃ -C ₄ ketones, aldehydes C ₂ -C ₄ and mixtures thereof.
The aqueous medium (water and optionally the water-miscible solvent) may be present in a content ranging from 0.1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 1% to 80% by weight. % in weight

Emulsifying system

According to the invention, an emulsifying system suitably chosen for obtaining an oil-in-water or wax-in-water emulsion is used.
The compositions according to the invention may contain emulsifying surfactants present in particular in a proportion ranging from 0.1 to 40%, and better still from 0.3% to 20% by weight relative to the total weight of the composition.

• les sels d'acides gras en C₁₆-C₃₀ notamment ceux dérivant des amines, comme le stéarate de triéthanolamine et/ou le stéarate d'amino-2 méthyl-2 propane di-ol-1,3;
• les sels d'acides gras polyoxyéthylénés notamment ceux dérivant des amines ou les sels alcalins, et leurs mélanges ;
• les esters phosphoriques et leurs sels tels que le "DEA oleth-10 phosphate" (Crodafos N 10N de la société CRODA) ;
• les sulfosuccinates tels que le "Disodium PEG-5 citrate lauryl sulfosuccinate" et le "Disodium ricinoleamido MEA sulfosuccinate"
• les alkyléthersulfates tels que le lauryl éther sulfate de sodium;
• les iséthionates ;
• les acylglutamates tels que le "Disodium hydrogenated tallow glutamate" (AMISOFT HS-21 R commercialisé par la société AJINOMOTO) et leurs mélanges.

Conviennent tout particulièrement à l'invention, le stéarate de triéthanolamine et/ou le stéarate d'amino-2 méthyl-2 propane di-ol-1,3. Ce dernier est généralement obtenu par simple mélange de l'acide stéarique avec de la triéthanolamine et/ou de l'amino-2 méthyl-2 propane di-ol-1,3.
D'une manière générale, les compositions selon l'invention peuvent contenir de 0,1 à 30 % en poids, en particulier de 0,5 à 20 % en poids voire de 1 à 15 % en poids de tensioactif anionique par rapport au poids total de la composition.The ionic surfactants used in the context of the present invention may be anionic, cationic or nonionic or amphoteric. However, generally, the choice of at least one anionic surfactant is preferred.
As a representative of the anionic surfactants that are suitable for the invention, mention may be made more particularly of:

• salts of C ₁₆ -C ₃₀ fatty acids, especially those derived from amines, such as triethanolamine stearate and / or 2-amino-2-methylpropane-1,3-diol stearate;
• salts of polyoxyethylenated fatty acids, in particular those derived from amines or alkaline salts, and mixtures thereof;
• phosphoric esters and their salts such as "DEA oleth-10 phosphate" (Crodafos N 10N from CRODA);
• sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate"
• alkyl ether sulfates such as sodium lauryl ether sulfate;
• isethionates;
• acylglutamates such as "Disodium hydrogenated tallow glutamate" (AMISOFT HS-21 R marketed by the company AJINOMOTO) and mixtures thereof.

Triethanolamine stearate and / or 2-amino-2-methylpropane diol-1,3 stearate are particularly suitable for the invention. The latter is generally obtained by simple mixing of stearic acid with triethanolamine and / or 2-amino-2-methylpropane di-1,3-ol.
In general, the compositions according to the invention may contain from 0.1 to 30% by weight, in particular from 0.5 to 20% by weight, or even from 1 to 15% by weight of anionic surfactant relative to the weight total of the composition.

• les alkyl-imidazolidinium tels que l'étho-sulfate d'isostéaryl-éthylimidonium,
• les sels d'ammonium tels que le chlorure de N,N,N-triméthyl-1-docosanaminium (chlorure de Behentrimonium).

As representative of cationic surfactants, mention may be made in particular of:

• alkyl imidazolidiniums such as isostearyl ethylimidonium ethosulphate,
• ammonium salts such as N, N, N-trimethyl-1-docosanaminium chloride (Behentrimonium chloride).

The composition according to the invention may further comprise at least one nonionic or amphoteric surfactant. Reference can be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", Vol. 22, p. 333-432, ^3rd edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular p. 347-377 of this reference, for anionic, amphoteric and nonionic surfactants.

Fatty phase

For the purposes of the invention, the term "fatty phase" means a phase composed of one or more non-aqueous bodies which are liquid or solid at room temperature (25 ° C.), generally compatible with one another, such as waxes, pasty fatty substances, oils, oils thickened by a structuring agent and mixtures thereof. The surfactants as described above are not part of the fatty phase.

Thus, the fatty phase of the composition according to the invention comprises at least one fatty alcohol wax and optionally an additional wax as described above.

The fatty phase advantageously has a hardness of less than or equal to 6 MPa, for example ranging from 0.5 to 6 MPa, preferably from 0.7 to 4 MPa and better still from 0.8 to 3 MPa.

The fatty phase may represent from 5% to 60% by weight relative to the total weight of the composition, preferably from 10% to 50% and better still from 15% to 40% by weight.

Oils

The composition according to the invention may in particular comprise one or more oils.
The oil may be chosen from volatile oils and / or non-volatile oils, and mixtures thereof. The composition advantageously comprises at least one volatile oil.

The oil may be present in the composition according to the invention in a content ranging from 0.1% to 60% by weight, preferably from 0.1% to 30% by weight relative to the total weight of the composition.

For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or the keratin fiber in less than one hour, at ambient temperature and atmospheric pressure. The volatile organic solvent (s) and the volatile oils of the invention are organic solvents and volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 0 to 13 Pa at 40 000 Pa (10 ^-3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa at 1300 Pa (0.01 to 10 mmHg).
By "non-volatile oil" is meant an oil remaining on the skin or the keratin fiber at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 ^-3 mm Hg (0.13 Pa). .
These oils may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof.
The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and phosphorus atoms. The volatile hydrocarbon oils may be chosen from hydrocarbon-based oils having 8 to 16 carbon atoms, and especially C8-C16 branched alkanes such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane ( also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopars' or permetyls, branched C8-C16 esters, isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, especially those sold under the name Shell Solt by Shell, can also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.
As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, especially those having a viscosity ≤ 8 centistokes (8 10 ^-6 m ² / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally having alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethylisiloxane, octamethyltrisiloxane and decamethyl tetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

où R représente un groupe alkyle comprenant de 2 à 4 atomes de carbone et dont un ou plusieurs atomes d'hydrogène peuvent être substitués par un atome de fluor ou de chlore.
Parmi les huiles de formule générale (I), on peut citer :

• le 3-butyl 1,1,1,3,5,5,5-heptaméthyl trisiloxane,
• le 3-propyl 1,1,1,3,5,5,5-heptaméthyl trisiloxane, et
• le 3-éthyl 1,1,1,3,5,5,5-heptaméthyl trisiloxane,
• correspondant aux huiles de formule (I) pour lesquelles R est respectivement un groupe butyle, un groupe propyle ou un groupe éthyle.

On peut également utiliser des solvants volatils fluorés tels que le nonafluorométhoxybutane ou le perfluorométhylcyclopentane.It is also possible to mention linear alkyltrisiloxane linear oils of general formula (I)

where R represents an alkyl group comprising from 2 to 4 carbon atoms and one or more hydrogen atoms of which may be substituted by a fluorine or chlorine atom.
Among the oils of general formula (I), mention may be made of:

• 3-butyl 1,1,1,3,5,5,5-heptamethyltrisiloxane,
• 3-propyl 1,1,1,3,5,5,5-heptamethyltrisiloxane, and
• 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,
• corresponding to the oils of formula (I) for which R is respectively a butyl group, a propyl group or an ethyl group.

It is also possible to use volatile fluorinated solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane.

It is also possible to use volatile fluorinated solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane.

• les huiles hydrocarbonées d'origine végétale telles que les triesters d'acides gras et de glycérol dont les acides gras peuvent avoir des longueurs de chaînes variées de C4 à C24, ces dernières pouvant être linéaires ou ramifiées, saturées ou insaturées ; ces huiles sont notamment les huiles de germe de blé, de tournesol, de pépins de raisin, de sésame, de maïs, d'abricot, de ricin, de karité, d'avocat, d'olive, de soja, l'huile d'amande douce, de palme, de colza, de coton, de noisette, de macadamia, de jojoba, de luzerne, de pavot, de potimarron, de sésame, de courge, de colza, de cassis, d'onagre, de millet, d'orge, de quinoa, de seigle, de carthame, de bancoulier, de passiflore, de rosier muscat ; ou encore les triglycérides des acides caprylique/caprique comme ceux vendus par la société Stéarineries Dubois ou ceux vendus sous les dénominations Miglyol 810, 812 et 818 par la société Dynamit Nobel,
• les éthers de synthèse ayant de 10 à 40 atomes de carbone ;
• les hydrocarbures linéaires ou ramifiés, d'origine minérale ou synthétique tels que la vaseline, les polydécènes, le polyisobutène hydrogéné tel que le parléam, le squalane, et leurs mélanges;
• les esters de synthèse comme les huiles de formule R1 COOR2 dans laquelle R1 représente le reste d'un acide gras linéaire ou ramifié comportant de 1 à 40 atomes de carbone et R2 représente une chaîne hydrocarbonée notamment ramifiée contenant de 1 à 40 atomes de carbone à condition que R5 + R6 soit ≥ 10, comme par exemple l'huile de Purcellin (octanoate de cétostéaryle), le myristate d'isopropyle, le palmitate d'isopropyle, le benzoate d'alcool en C12 à C15, le laurate d'hexyle, l'adipate de diisopropyle, l'isononanoate d'isononyle, le palmitate de 2-éthyl-hexyle, l'isostéarate d'isostéarate, des octanoates, décanoates ou ricinoléates d'alcools ou de polyalcools comme le dioctanoate de propylène glycol ; les esters hydroxylés comme le lactate d'isostéaryle, le malate de diisostéaryle ; et les esters du pentaérythritol ;
• les alcools gras liquides à température ambiante à chaîne carbonée ramifiée et/ou insaturée ayant de 12 à 26 atomes de carbone comme l'octyl dodécanol, l'alcool isostéarylique, l'alcool oléique, le 2-hexyldécanol, le 2-butyloctanol, le 2-undécylpentadécanol ;
• les acides gras supérieurs tels que l'acide oléique, l'acide linoléique, l'acide linolénique ;
• les carbonates,
• les acétales,
• les citrates,
• et leurs mélanges.

The composition may also comprise at least one non-volatile oil, and in particular chosen from non-volatile hydrocarbon and / or silicone and / or fluorinated oils.
As non-volatile hydrocarbon oil, mention may notably be made of:

• hydrocarbon oils of plant origin such as triesters of fatty acids and of glycerol whose fatty acids may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils include wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, pumpkin, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passiflora, muscat rose; or the caprylic / capric acid triglycerides, such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel,
• synthetic ethers having from 10 to 40 carbon atoms;
• linear or branched hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof;
• synthetic esters such as the oils of formula R 1 COOR 2 in which R 1 represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon chain, in particular branched, containing from 1 to 40 carbon atoms at provided that R5 + R6 is ≥ 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoate, hexyl laurate diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters;
• branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
• higher fatty acids such as oleic acid, linoleic acid, linolenic acid;
• the carbonates,
• acetals,
• citrates,
• and their mixtures.

The non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates;
The fluorinated oils that can be used in the invention are in particular fluorosilicone oils, fluorinated polyethers and fluorinated silicones as described in document EP-A-847752.

Structuring agent

The structuring agent of the oil (s), if present, may be chosen from semi-crystalline polymers, lipophilic gelling agents and mixtures thereof.

By polymer is meant compounds having at least two units, preferably at least 3 units and especially at least 10 repeating units. By "semi-crystalline polymer" is meant polymers having a crystallizable portion, a pendant crystallizable chain or a crystallizable block in the backbone, and an amorphous portion in the backbone and having a first-order reversible phase change temperature, in which particular fusion (solid-liquid transition). When the crystallizable portion is in the form of a crystallizable block of the polymer backbone, the amorphous portion of the polymer is in the form of an amorphous sequence; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. By "sequence" is generally meant at least 5 identical repetition patterns. The crystallizable sequence (s) are then of a different chemical nature from the amorphous sequence (s).
The semi-crystalline polymer has a melting point greater than or equal to 30 ° C (especially from 30 ° C to 80 ° C), preferably from 30 ° C to 60 ° C. This melting temperature is a first order change of state temperature.
This melting temperature can be measured by any known method and in particular using a differential scanning calorimeter (DSC).
Advantageously, the semi-crystalline polymer or polymers to which the invention applies have a number average molecular mass greater than or equal to 1,000. Advantageously, the semi-crystalline polymer (s) of the composition of the invention have a number-average molecular mass M n ranging from 2,000 to 800,000, preferably from 3,000 to 500,000, more preferably from 4,000 to 150,000. especially less than 100,000, and more preferably from 4,000 to 99,000. Preferably, they have a number average molecular weight greater than 5,600, for example from 5,700 to 99,000. By "chain or crystallizable block", For the purposes of the invention, it is intended to mean a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state reversibly, depending on whether it is above or below the melting point. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one of the repeating units of the polymer. Advantageously, the "crystallizable pendant chain" can be a chain comprising at least 6 carbon atoms.
The semi-crystalline polymer may be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, homopolymers and copolymers bearing at least one crystallizable side chain per repeating unit, and mixtures thereof.
Such polymers are described for example in EP 1396259.
According to a more particular embodiment of the invention, the polymer is derived from a crystallizable chain monomer chosen from saturated C ₁₄ -C ₂₂ alkyl (meth) acrylates.
As a particular example of a structuring semicrystalline polymer that may be used in the composition according to the invention, mention may be made of the Intelimer® products from Landec, described in the brochure "Intelimer® Polymers", Landec IP22 (Rev. 4-97 ). These polymers are in solid form at ambient temperature (25 ° C.). They carry crystallizable side chains.

• des groupements triméthylsiloxyle, qui sont notamment obtenus par traitement de silice pyrogénée en présence de l'hexaméthyldisilazane. Des silices ainsi traitées sont dénommées « Silica silylate » selon le CTFA (6^ème édition, 1995). Elles sont par exemple commercialisées sous les références Aerosil R812® par la société DEGUSSA, CAB-O-SIL TS-530® par la société CABOT,
• des groupements diméthylsilyloxyle ou polydiméthylsiloxane, qui sont notamment obtenus par traitement de silice pyrogénée en présence de polydiméthylsiloxane ou du diméthyldichlorosilane. Des silices ainsi traitées sont dénommées "Silica diméthyl silylate" selon le CTFA (6^ème édition, 1995). Elles sont par exemple commercialisées sous les références Aerosil R972® , et Aerosil R974® par la société DEGUSSA, CAB-O-SIL TS-610® et CAB-O-SIL TS-720® par la société CABOT.
  La silice pyrogénée hydrophobe présente en particulier une taille de particules pouvant être nanométrique à micrométrique, par exemple allant d'environ de 5 à 200 nm.
  Les gélifiants lipophiles organiques polymériques sont par exemple les organopolysiloxanes élastomériques partiellement ou totalement réticulés, de structure tridimensionnelle, comme ceux commercialisés sous les dénominations de KSG6® , KSG16® et de KSG18® par la société SHIN-ETSU, de Trefil E-505C® et Trefil E-506C® par la société DOW-CORNING, de Gransil SR-CYC® , SR DMF10® , SR-DC556® , SR 5CYC gel® , SR DMF 10 gel® et de SR DC 556 gel® par la société GRANT INDUSTRIES, de SF 1204® et de JK 113® par la société GENERAL ELECTRIC ; l'éthylcellulose comme celle vendue sous la dénomination Ethocel® par la société DOW CHEMICAL ; les polycondensats de type polyamide résultant de la condensation entre (α) au moins un acide choisi parmi les acides dicarboxyliques comprenant au moins 32 atomes de carbone tels que les acides gras dimères et (β) un alkylène diamine et en particulier l'éthylène diamine, dans lequel le polymère polyamide comprend au moins un groupe acide carboxylique terminal estérifié ou amidifié avec au moins un mono alcool ou une mono amine comprenant de 12 à 30 atomes de carbone linéaires et saturés, et en particulier, les copolymères d'éthylène diamine/dilinoléate de stéaryle tel que celui commercialisé sous la dénomination Uniclear 100 VG® par la société ARIZONA CHEMICAL ; les galactommananes comportant de un à six, et en particulier de deux à quatre, groupes hydroxyle par ose, substitués par une chaîne alkyle saturée ou non, comme la gomme de guar alkylée par des chaînes alkyle en C₁ à C₆, et en particulier en C₁ à C₃ et leurs mélanges. Les copolymères séquencés de type "dibloc", "tribloc" ou "radial" du type polystyrène/polyisoprène, polystyrène/polybutadiène tels que ceux commercialisés sous la dénomination Luvitol HSB® par la société BASF, du type polystyrène/copoly(éthylène-propylène) tels que ceux commercialisés sous la dénomination de Kraton® par la société SHELL CHEMICAL CO ou encore du type polystyrène/copoly(éthylène-butylène), les mélanges de copolymères tribloc et radial (en étoile) dans l'isododécane tels que ceux commercialisé par la société PENRECO sous la dénomination Versagel® comme par exemple le mélange de copolymère tribloc butylène/éthylène/styrène et de copolymère étoile éthylène/propylène/styrène dans l'isododécane (Versagel M 5960).
  On peut également utiliser les polyamides siliconés du type polyorganosiloxane tels que ceux décrits dans les documents US-A-5 874 069, US-A-5,919,441, US-A-6,051,216 et US-A-5,981,680.
  Ces polymères siliconés peuvent appartenir aux deux familles suivantes:

• des polyorganosiloxanes comportant au moins deux groupes capables d'établir des interactions hydrogène, ces deux groupes étant situés dans la chaîne du polymère, et/ou
• des polyorganosiloxanes comportant au moins deux groupes capables d'établir des interactions hydrogène, ces deux groupes étant situés sur des greffons ou ramifications.
  Parmi les gélifiants lipophiles pouvant être utilisés dans les compositions selon l'invention, on peut encore citer les esters de dextrine et d'acide gras, tels que les palmitates de dextrine, notamment tels que ceux commercialisés sous les dénominations Rheopearl TL® ou Rheopearl KL® par la société CHIBA FLOUR.

The gelling agents that may be used in the compositions according to the invention may be organic or inorganic, polymeric or molecular lipophilic gelling agents.
As inorganic lipophilic gelling agents, there may be mentioned optionally modified clays, such as hectorites modified with a C ₁₀ to C ₂₂ fatty acid ammonium chloride, such as hectorite modified with di-stearyl dimethyl ammonium chloride such as that, for example, that sold under the name of Bentone 38V® by the company ELEMENTIS.
It is also possible to mention fumed silica optionally treated hydrophobic surface whose particle size is less than 1 micron. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. We can substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups can be:

• trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are named "Silica Silylate" according to the CTFA ^(6th edition, 1995). They are for example marketed under the references Aerosil R812® by the company DEGUSSA, CAB-O-SIL TS-530® by CABOT,
• dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl Silylate" according to the CTFA ^(6th edition, 1995). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by CABOT.
  The hydrophobic fumed silica has in particular a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm.
  Polymeric organic lipophilic gelling agents are, for example, partially or fully crosslinked elastomeric organopolysiloxanes of three-dimensional structure, such as those marketed under the names KSG6®, KSG16® and KSG18® by the company SHIN-ETSU, by Trefil E-505C® and Trefil E-506C® by DOW-CORNING, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by GRANT INDUSTRIES , SF 1204® and JK 113® by the company GENERAL ELECTRIC; ethylcellulose such as that sold under the name Ethocel® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between ( α ) at least one acid selected from dicarboxylic acids comprising at least 32 carbon atoms such as dimeric fatty acids and (β) an alkylene diamine and in particular ethylene diamine, wherein the polyamide polymer comprises at least one terminal carboxylic acid group esterified or amidated with at least one monohydric alcohol or a monoamine comprising from 12 to 30 linear and saturated carbon atoms, and in particular ethylene diamine / dilinoleate copolymers stearyl such as that marketed under the name Uniclear 100 VG® by ARIZONA CHEMICAL; galactomannans having from one to six, and in particular from two to four, hydroxyl groups per sac, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated with C ₁ to C ₆ alkyl chains, and in particular C ₁ to C _3, and mixtures thereof. Block copolymers of the "diblock", "triblock" or "radial" type of the polystyrene / polyisoprene, polystyrene / polybutadiene type, such as those sold under the name Luvitol HSB® by BASF, of the polystyrene / copoly (ethylene-propylene) type such as those sold under the name Kraton® by Shell Chemical Co., or else from the polystyrene / copoly (ethylene-butylene) type, mixtures of triblock and radial (star) copolymers in isododecane, such as those marketed by the company PENRECO company under the name Versagel® such as, for example, the mixture of butylene / ethylene / styrene triblock copolymer and ethylene / propylene / styrene star copolymer in isododecane (Versagel M 5960).
  It is also possible to use silicone polyamides of the polyorganosiloxane type such as those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680.
  These silicone polymers can belong to the following two families:

• polyorganosiloxanes having at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and / or
• polyorganosiloxanes having at least two groups capable of establishing hydrogen interactions, both groups being located on grafts or branches.
  Among the lipophilic gelling agents that can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those sold under the names Rheopearl TL® or Rheopearl KL. ® by the company CHIBA FLOUR.

additives

The composition according to the invention may also comprise a dyestuff such as pulverulent dyestuffs, liposoluble dyes and water-soluble dyes. This dyestuff may be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition.

The pulverulent dyestuffs may be chosen from pigments and nacres.

The pigments may be white or colored, mineral and / or organic, coated or uncoated. Among the inorganic pigments, titanium dioxide, optionally surface-treated, oxides of zirconium, zinc or cerium, as well as oxides of iron or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.

The nacres may be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

Liposoluble dyes are, for example, Sudan red, D & C Red 17, D & C Green 6, β-carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet 2, D & C orange 5, the yellow quinoline, the annatto. The water-soluble dyes are, for example, beet juice, methylene blue, culinary disodium salt, disodium salt of alizarin green, quinoline yellow, trisodium salt of amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, the disodium salt of fuchsin, xanthophyll.

The composition according to the invention may also comprise fillers chosen from those well known to those skilled in the art and commonly used in cosmetic compositions. The fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders such as Nylon® (Orgasol from Atochem), poly-β-alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon® , lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as ExpanceL® (Nobel Industry), acrylic powders such as polytrap® (Dow Corning), polymethyl methacrylate particles and silicone resin microspheres (eg, Toshiba Tospearls®), precipitated calcium carbonate, magnesium carbonate and hydrocyanate, hydroxyapatite, microspheres hollow silicates (MAPRECOS SILICA BEADS®), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
The fillers can represent from 0.1 to 25%, and better still from 1 to 20% by weight, of the total weight of the composition.

The composition of the invention may furthermore comprise any additive usually used in cosmetics, such as antioxidants, preservatives, perfumes, neutralizers, hydrophilic gelling agents, thickeners, vitamins, fibers and their mixtures.

Of course, those skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not or not substantially impaired by the addition envisaged.

• les homo- ou copolymères d'acides acrylique ou méthacrylique ou leurs sels et leurs esters et en particulier les produits vendus sous les dénominations VERSICOL F® ou VERSICOL K® par la société ALLIED COLLOID, UTRAHOLD 8® par la société CIBA-GEIGY, les acides polyacryliques de type SYNTHALEN K,
• les copolymères d'acide acrylique et d'acrylamide vendus sous la forme de leur sel de sodium sous les dénominations RETEN® par la société HERCULES, le polyméthacrylate de sodium vendu sous la dénomination DARVAN N°7® par la société VANDERBILT, les sels de sodium d'acides polyhydroxycarboxyliques vendus sous la dénomination HYDAGEN F® par la société HENKEL,
• les copolymères acide polyacryliques/acrylates d'alkyle de type PEMULEN,
• l'AMPS (Acide polyacrylamidométhyl propane sulfonique neutralisé partiellement à l'ammoniaque et hautement réticulé) commercialisé par la société CLARIANT,
• les copolymères AMPS/acrylamide de type SEPIGEL® ou SIMULGEL® commercialisés par la société SEPPIC, et
• les copolymères AMPS/méthacrylates d'alkyle polyoxyéthylénés (réticulés ou non), et leurs mélanges.

Les polymères filmogènes hydrosolubles cités plus haut peuvent également jouer le rôle de gélifiant hydrosoluble.
Le polymère gélifiant hydrosoluble peut être présent dans la composition selon l'invention en une teneur en matières sèches allant de 0,01 % à 60 % en poids, de préférence de 0,5 % à 40 % en poids, mieux de 1 % à 30 % en poids, voire de 5 à 20 % en poids par rapport au poids total de la composition.The hydrophilic gelling agents that can be used in the compositions according to the invention can be chosen from:

• homo- or copolymers of acrylic or methacrylic acids or their salts and esters and in particular the products sold under the names VERSICOL F® or VERSICOL K® by ALLIED COLLOID, UTRAHOLD 8® by CIBA-GEIGY, polyacrylic acids of SYNTHALEN K type,
• copolymers of acrylic acid and of acrylamide sold in the form of their sodium salt under the names RETEN® by the company HERCULES, sodium polymethacrylate sold under the name DARVAN No. 7® by the company Vanderbilt, the salts of sodium of polyhydroxycarboxylic acids sold under the name HYDAGEN F® by the company HENKEL,
• polyacrylic acid / alkyl acrylate copolymers of PEMULEN type,
• AMPS (polyacrylamidomethyl propanesulfonic acid partially neutralized with ammonia and highly crosslinked) marketed by the company CLARIANT,
• the AMPS / acrylamide copolymers of the SEPIGEL® or SIMULGEL® type marketed by the company SEPPIC, and
• polyoxyethylenated AMPS / alkyl methacrylate copolymers (crosslinked or otherwise), and mixtures thereof.

The water-soluble film-forming polymers mentioned above can also act as water-soluble gelling agent.
The water-soluble gelling polymer may be present in the composition according to the invention in a dry matter content ranging from 0.01% to 60% by weight, preferably from 0.5% to 40% by weight, better still from 1% to 30% by weight, or even 5 to 20% by weight relative to the total weight of the composition.

By "fiber" it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed. In particular, the L / D ratio (or form factor) is chosen in the range from 3.5 to 2500, preferably from 5 to 500, and more preferably from 5 to 150.
In particular, the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm.

The fibers that may be used in the composition of the invention may be chosen from rigid or non-rigid fibers, they may be of synthetic or natural, mineral or organic origin.
As fibers that can be used in the composition according to the invention, mention may be made of non-rigid fibers such as polyamide (Nylon®) fibers or rigid fibers such as polyimide-amide fibers, such as those sold under the name "KERMEL""," KERMEL TECH "by the company Rhodia or poly- (p-phenylene terephthalamide) (or aramid) sold especially under the name Kevlar® by the company DuPont de Nemours.

Preferably, the composition according to the invention is a mascara.

The compositions according to the invention may be prepared according to methods known to those skilled in the art.

The composition according to the invention may be packaged in a container defining at least one compartment which comprises said composition, said container being closed by a closure element.

The container is preferably associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from molding. Such combs are described for example in patent FR 2 796 529. The applicator may be integral with the container, as described for example in patent FR 2 761 959. Advantageously, the applicator is secured to a rod which same, is integral with the closure element.

The closure member may be coupled to the container by screwing. Alternatively, the coupling between the closure member and the container is other than by screwing, in particular via a bayonet mechanism, snap-fastening, or clamping. By "latching" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the position not elastically constrained of said portion after crossing the bead or cord.

The container may be at least partly made of thermoplastic material. Examples of thermoplastic materials include polypropylene or polyethylene.

Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).

The container is preferably equipped with a wiper arranged in the vicinity of the opening of the container. Such a wiper makes it possible to wipe the applicator and possibly the rod which it can be secured. Such a wiper is described, for example, in patent FR 2 792 618.

The contents of the aforementioned patents or patent applications are incorporated by reference in this application.

The following examples are presented for illustrative and not limiting of the invention.
The quantities indicated are in weight percentage and expressed in relation to the total weight of the composition, unless otherwise specified.

Example 1: Mascara

The following mascara can be prepared: Hydroxyethyl cellulose 1 triethanolamine 3.1 stearic acid 5.8 Alcohol Wax (Performacol 350 from NEW PHASE TECHNOLOGIES) 30 Water qs 100

Example 2 to 4: Mascaras

2 mascaras (Examples 3 and 4) are prepared according to the invention comprising a fatty alcohol wax (behenic alcohol) and a cellulosic polymer and a mascara according to the prior art (example 2) comprising a cellulosic polymer but no fatty alcohol wax. Example 2 (except invention) Example 3 Example 4 hydroxyethyl cellulose 1 1 1 triethanolamine 3.1 3.1 3.1 stearic acid 5.8 5.8 5.8 behenic alcohol 0 10 17 Sticky wax (Koster Keunen's Kester Wax K82P) 20 10 3 Water Qs 100 Qs 100 Qs 100

For each example, the load is measured in vitro.
The in vitro load is measured gravimetrically on 2 specimens of false eyelashes that are curved Caucasian hair (15 long hair of about 15 mm distributed over a distance of 1 cm).
The false eyelashes are makeup from below by performing 3x10 mascara passages spaced 2 minutes with product recovery between each set of 10.
The two test pieces are dried for 10 min at room temperature and weighed.

The charge at To (C _To ) of the sample before drying is determined, which corresponds to the load measured after drying (C _sec ) divided by the solids content of the composition (ES). $${\mathrm{VS}}_{\mathrm{T}\mathrm{o}}={\mathrm{VS}}_{\mathrm{dry}}/\mathrm{E}\mathrm{S}$$

We obtain the following results C _To Charge (in g) Example 2 0.0025 Example 3 0.0031 Example 4 0.0042

The compositions of Examples 3 and 4 according to the invention have a higher filler than the composition comprising no fatty alcohol wax. It is also noted that the load increases with the content of wax fatty alcohol.

Claims (26)

A keratinous fiber coating composition comprising a cosmetically acceptable aqueous medium characterized in that it comprises at least 3% of at least one fatty alcohol wax and at least one cellulosic polymer. Keratin fiber coating composition comprising a cosmetically acceptable aqueous medium characterized in that it comprises at least one fatty alcohol wax, at least one cellulosic polymer and at least one anionic surfactant. Composition according to Claim 1 or 2, characterized in that the cellulosic polymer is chosen from alkylcelluloses, hydroxyalkylcelluloses, carboxyalkylcelluloses and their mixtures. Composition according to one of Claims 1 to 3, characterized in that the cellulosic polymer is present in a solids content ranging from 0.1% to 30% by weight relative to the total weight of the composition, preferably from 0 to 30% by weight relative to the total weight of the composition. From 5% to 20% by weight, and more preferably from 1% to 15% by weight. Composition according to any one of the preceding claims, characterized in that the fatty alcohol wax is chosen from saturated or unsaturated, branched or unbranched fatty alcohols containing from 14 to 80 carbon atoms, or mixtures comprising at least 30% of said of fatty alcohols. Composition according to any one of the preceding claims, characterized in that the fatty alcohol wax is chosen from linear fatty alcohols comprising from 14 to 60 carbon atoms, preferably from 20 to 58 carbon atoms, the branched alcohols comprising from 24 to 20 carbon atoms. to 80 carbon atoms and mixtures thereof. Composition according to any one of the preceding claims, characterized in that the fatty alcohol wax represents from 3 to 50% by weight, preferably from 5 to 40%, better still from 7 to 30% by weight and even more preferably from 10 to 30% by weight. % by weight relative to the total weight of the composition. Composition according to one of the preceding claims, characterized in that it comprises at least one additional wax. Composition according to the preceding claim, characterized in that the additional wax is chosen from hydrocarbon-based waxes such as beeswax, lanolin wax, lemon wax, orange wax and Chinese insect waxes; rice wax, carnauba wax, candellila wax, ouricurry wax, cork fiber wax, sugar cane wax, japanese wax, berry wax, shellac wax and sumac wax; montan wax, microcrystalline waxes, paraffins, ozokerite; polyethylene waxes, polymethylene waxes, waxes obtained by the Fisher-Tropsch synthesis, waxy copolymers and their esters, and waxes obtained by catalytic hydrogenation of animal or vegetable oils with linear or branched C8 fatty chains. -C32, silicone waxes, fluorinated waxes and mixtures thereof. Composition according to Claim 8 or 9, characterized in that the additional wax has a hardness less than or equal to 4 MPa, preferably less than or equal to 3.5 MPa. Composition according to any one of Claims 8 to 10, characterized in that the additional wax is chosen from waxes having a tack greater than or equal to 0.1 Ns. Composition according to any one of Claims 8 to 11, characterized in that the additional wax is a C ₂₀ -C ₄₀ alkyl (hydroxystearoyloxy) stearate. Composition according to any one of Claims 8 to 12, characterized in that the additional wax is present in a content ranging from 5% to 50% by weight relative to the total weight of the composition, preferably from 5% to 40% by weight. weight, more particularly from 10 to 35% by weight. Composition according to any one of Claims 1 and 3 to 13, characterized in that it comprises at least one anionic surfactant. Composition according to Claim 2 or 14, characterized in that the said anionic surfactant is chosen from the salts of C ₁₆ -C ₃₀ fatty acids; fatty acid salts polyoxyethoxylenes; phosphoric esters and their salts; alkyl ether sulphates; sulfosuccinates; isethionates and acylglutamates and mixtures thereof. Composition according to Claim 14 or 15, characterized in that the anionic surfactant comprises at least triethanolamine stearate and / or 2-amino-2-methyl-2-propane diol-1,3 stearate. Composition according to any one of Claims 14 to 16, characterized in that the anionic surfactant is present in a proportion of from 0.01 to 30% by weight and in particular from 0.1 to 15% by weight of the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it comprises an additional film-forming polymer chosen from synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures. Composition according to Claim 18, characterized in that the additional film-forming polymer is present in a solids content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably from 0.5% to 40% by weight, and more preferably from 1% to 30% by weight. Composition according to any one of the preceding claims, characterized in that an aqueous medium is present in a content ranging from 0.1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 1% to 80% by weight. % in weight. Composition according to one of the preceding claims, characterized in that it comprises a dyestuff. Composition according to Claim 21, characterized in that the dyestuff is present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition. Composition according to one of claims 1 to 22, characterized in that it is a mascara. Use of a composition according to one of claims 1 to 23, for obtaining makeup charging keratinous fibers and in particular eyelashes and / or a smooth and homogeneous deposit on said fibers. Use of the combination of at least one fatty alcohol wax and a cellulosic polymer to obtain a makeup charging keratinous fibers including eyelashes and eyebrows and / or a smooth and homogeneous deposit on said fibers. Cosmetic process for treating or making up keratin fibers, comprising applying to said keratin fibers a composition according to any one of Claims 1 to 23.